Process for breaking petroleum emulsions employing certain oxyalkylated polyepoxide-treated amine-modified thermoplastic phenol-aldehyde resins



Unite T. States Melvin De Groote, University City, and Kwan-Ting Shen, Brentwood, Mo., assignors to Petrolite Corporation, Wilmington, DeL, a corporation of Delaware No Drawing. Application June 26, 1953, Serial No. 364,503

20 Claims. (Cl. 252-338) The present invention is a continuation-in-part of our co-pending application, Serial No. 338,575, filed February 24, 1953.

Our invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous .phase of the emulsion.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

The present invention is concerned with the breaking of emulsions of the water-in-oil type by subjecting them to the action of products obtained by a three-step manufacturing process involving (1) condensing certain phenol aldehyde resins, hereinafter described in .detail, with certain basic non-hydroxylated polyamines, hereinafter described in detail, and formaldehyde; (2) oxyalkylation of the condensation product with certain phenolic polyepoxides, hereinafter described in detail; and (3) oxyalkylation of the previously oxyalkylated resin condensate with certain monoepoxides, also hereinafter described in detail.

For a number of reasons it is usually most desirable to use the diepoxide type of polyepoxide. In preparing diepox ides or the low mo'la'l polymers -tne .usuallyobtains 1) Compounds of the following formula:

HzC---CH-CH2OQ 0 (CH3): i:

and

(2) cogenerically associated compounds formed in the preparation of (l) preceding,

with the proviso that it consists principally of the'rnon'omer as distinguished from other cogeners.

Notwithstanding the fact that subsequent data will be presented in considerable detail, yet'the description atent O becomes somewhat involved and certain facts should be kept in mind. The epoxides, and particularly the diepoxides may have no connecting bridge between the phenolic nuclei as in the case of a diphenyl derivative a or may have a variety of connecting bridges, i. e., divalent linking radicals. Our preference is that either diphenyl compounds be employed or else compounds where the divalent link is obtained by the removal of a carbonyl oxygen atom as derived from a ketone or aldehyde.

If it were not for the expense involved in preparing and purifying the monomer we would prefer it to any other form, i. e., in preference to the polymer of mixture of polymer and monomer.

Stated another way, we would prefer to use materials of the kind described, for example, in U. S. Patent No.

2,530,353, dated November 14, 1950. Said patent describes compounds having the general formula wherein R is an aliphatic hydrocarbon bridge, each n independently has one of the values .0 and 1, and X is an alkyl radical containing from T1 to 4 carbon atoms.

The compounds having twooxirane rings and employed for combination with the reactive amine-modified phenolaldehyde resin condensates ,as herein described are characterized by the following formulaand cogenerically associated compounds formed in their preparation:

the divalent 0 ll C radical, the divalent sulfone radical, and the divalent monosulfide radical --S, the divalent radical .and the divalent disulfide radical -SS; and R10 is the divalent radical obtained by the elimination of a 'hydroxyl hydrogen atom and a nuclear hydrogen atom from the phenol in which R, .R", and R represent hydrogen andvhydrocarbon-substituents of .the aromaticnucleus, said substituent member having not over 18 carbon atoms; In rep- .resents aninteger including zero and 1 ,and n represents ;a whole, number notgreater'than 3. The above mentioned compounds and those. cogenerically associated compounds formed in theirpreparation arethermoplastic and organic solvent-soluble. Reference to being thermoplastic characterizes products asbeing liquids atordinary temperature 70 or readily convertibleto'liquids-by merely heating below -thegpoint of pyrolysis and thus differentiates them from infusible resins. Reference to being soluble in an organic solvent means any of the usual organic solvents, such as alcohols, ketones, esters, ethers, mixed solvents, etc. Reference to solubility is merely to difierentiate from a reactant which is not soluble and might be not only insoluble but also infusible. Furthermore, solubility is a factor insofar that it is sometimes desirable to dilute the compound containing the epoxy rings before reacting with the amine resin condensate. In such instances, of course, the solvent selected would have to be one which is not susceptible to oxyalkylation, as, for example, kerosene, benzene, toluene, dioxane, various ketones, chlorinated solvents, dibutyl ether, dihexyl ether, ethyleneglycol diethylether, diethyleneglycol diethylether, and dimethoxytetraethyleneglycol.

The expression epoxy is not usually limited to the 1,2-epoxy ring. The 1,2-epoxy ring is sometimes referred to as the oxirane ring to distinguish it from other epoxy rings. Hereinafter the Word epoxy unless indicated otherwise, will be used to mean the oxirane ring, i. e., the 1,2-epoxy ring. Furthermore, where a compound has two or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2-epoxide rings or oxirane rings in the alpha-omega position. This is a departure, of course, from the standpoint of strictly formal nomenclature as in the example of the simplest diepoxide which contains at least 4 carbon atoms and is formally described as l,2-epoxy-3,4- epoxybutane (l,2-3,4 diepoxybutane).

Having obtained a reactant having generally 2 epoxy rings as depicted in the last formula preceding, or low molal polymers thereof, it becomes obvious the reaction can take place with any amine-modified phenol-aldehyde resin by virtue of the fact that there are always present reactive hydroxyl groups which are part of the phenolic nuclei and there may be present reactive hydrogen atoms attached to a nitrogen atom, or an oxygen atom, depending on the presence of a hydroxylated group or second-- ary amino group.

To illustrate the products which represent the subject matter of the present invention reference will be made to a reaction involving a mole of the oxyalkylating agent, i. e., the compound having 2 oxirane rings and an amine condensate. Proceeding with the example previously described it is obvious the reaction ratio of 2 moles of the amine condensate to one mole of the oxyalkylating agent gives a product which may be indicated as follows:

shaken with 5 to 20 times their weight of 5% gluconie acid at ordinary temperature and show at least some tendency towards being self-dispersing. The solvent which is generally tried is xylene. If xylene alone does not serve then a mixture of xylene and methanol, for instance, 80 parts of xylene and 20 parts of methanol, or 70 parts of xylene and 30 parts of methanol, can be used. Sometimes it is desirable to add a smallarnount of acetone to the xylene-methanol mixture, for instance, 5% to 10% of acetone.

A mere examination of the nature of the products before and after treatment with the polyepoxide reveals that the polyepoxide by and large introduces increased hydrophobe character or, inversely, causes a decrease in hydrophile character. However, the solubility characteristics of the final product, i. e., the product obtained by oxyalkylation of a monoepoxide, may vary all over the map. This is perfectly understandable because ethylene oxide, glycide, and to a lesser extent methyl glycide, introduce predominantly hydrophile character, or propylene oxide and more especially butylene oxide, introduce primarily hydrophobe character. A mixture of the various oxides will produce a balancing in solubility characteristics or in the hydrophile-hydrophobe character so as to be about the same as prior to oxyalkylation with the monoepoxide.

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the water-in-oil type, we particularly prefer to use those which as such or in the form of the free. base or hydrate, i. e., combination with water or particularly in the form of a low molal organic acid salt such as the gluconates or the acetate or hydroxy acetate, have sufiiciently hydrophile character to at least meet the test set forth inU. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various oxyalkylated condensation products as such or in the form of the free base or in the form of theacetate, may not necessarily j a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve (condensate) in which the various characters have their previous significance and the characterization condensate is simply an abbreviation for the condensate which is described in greater detail subsequently.

Such intermediate product in turn also must be soluble but solubility is not limited to an organic solvent but may include water, or forthat matter, a solutionof water containing an acid such as hydrochloric acid, acetic acid, hydroxyacetic acid, etc. In other words, the nitrogen groups present, whether two or more, may or may not be significantly basic and it is immaterial whether aqueous solubility represents an anhydro base or the free base (combination with water) or a salt form which has the acetate, chloride, etc. The purpose in this instance is to differentiate from insoluble resinous materials, particularly those resulting from gelation or cross-linking. Not only does this properly serve to differentiate from instances where an insoluble material is desired, but also serves to emphasize the fact that in many instances the preferred compounds have distinct Water-solubility or are distinctly dispersible in 5% gluconic acid. For instance, the products freed from any solvent can 'be (condensate) the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

.. taining low molal polymeric epoxides as well as the mono rner and includes Table II;

Part 3, Subdivision C, is concerned with miscellaneous phenolic reactants suitable for diepoxide preparation;

Part 4 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield the amine-modified resin;

Part 5 is concerned with basic nonhydroxylated polyamines having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, and substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and

Part 6 is concerned with reactions involving the resin, the amine, and formaldehyde to produce specific products or compounds which are then subjected to reaction with polyepoxides;

Part 7 is concerned with the reactions involving the two preceding types of materials and examples obtained by such reaction. Generally speaking, this involves nothiug more than a reaction between 2 moles of a previously prepared amine-modified phenol-aldehyde resin condensate as described, and one mole of a polyepoxide so as to yield a new and larger resin molecule, or comparable product;

Part 8 is concerned with the use of a monoepoxide in oxyalkylating the products described in Part 7, preceding, i. e., those derived by means of reaction between a polyepoxide and an aminemodified phenol-aldehyde resin :as described;

Part 9 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products.

PART 1 As will be pointed out subsequently, the preparation of polyepoxides may include the formation of a small amount of material having more than two epoxide groups per molecule. If such compounds are formed they are perfectly suitable except to the extent they may tend to produce ultimate reaction products which are not solventsoluble liquids or low-melting solids. Indeed, they tend to form thermosetting resins or insoluble materials. Thus, the specific objective by and large is to produce diepoxides as free as possible from any monoepoxides and as free as possible from polyepoxides in which there are more than two epoxide groups per molecule. Thus, for practical purposes what is said hereinafter is largely limited to polyepoxides in the form of diepoxides.

As has been pointed out previously one of the reactants employed is a diepoxide reactant. It is generally obtained from phenol (hydroxybenzene) or substituted phenol. The ordinary or conventional manufacture of the epoxides usually results in the formation of a co-generic mixture as explained subsequently. Preparation of the monomer or separation of the monomer from the remaining mass of the co-generic mixture is usually expensive. If monomers were available commercially at a low cost, or if they could be prepared without added expense for separation, our preference would be to use the monomer. Certain monomers have been prepared and described in the literature and will be referred to subsequently. However, from a practical standpoint one must weigh the advantage, if any, that the monomer has over other low molal polymers from a cost standpoint; thus, we have found that one might as well attempt to prepare a monomer and fully recognize that there may be present, and probably invariably are present, other low molal polymers in comparatively small amounts. Thus, the materials which are most apt to be used for practical reasons are either monomers with some small amounts of polymers present or mixtures which have a substantial amount of polymers present. Indeed, the mixture can be prepared free from monomers and still be satisfactory. Briefly, then, our preference is to use the monomer or the monomer with the minimum amount of higher polymers.

It has been pointed out previously that the phenolic 6 nuclei in the epoxide reactant may be directly united, of united through a variety of divalent radicals. Actually, it is our preference to use those which are commercially available and for most practical purposes it means instances where the phenolic nuclei are either united directly without any intervening linking radical, or else united by a ketone residue or formaldehyde residue. The commercial bis-phenols available now in the open market illustrate one class. The diphenyl derivatives illustrate a second class, and'the materials obtained by reacting substituted monofunctional phenols with an aldehyde illus trate the third class. All the various known classes may be used but our preference rests with these classes due to their availability and ease of preparation, and also due to the fact that the cost is lower than in other examples.

Although the diepoxide reactants can be produced in more than one way, as pointed out elsewhere, our preferonce is to produce them by means of the epichlorohydrin reaction referred to in detail subsequently.

One epoxide which can be purchased in the open market and contains only a modest amount of polymers corresponds to the derivative of bis-phenol A. It can be used as such, or the monomer can be separated by an added step which involves additional expense. This compound of the following structure is preferred as the epoxide reactant and will be used for illustration repeatedly with the full understanding that any of the other epoxides described are equally satisfactory, or that the higher polymers are satisfactory, or that mixtures of the monomer and higher polymers are satisfactory. The formula for this compound is o CH3 0 Reference has just been made to bis-phenol A and a suitable epoxide derived therefrom. Bis-phenol A is dihydroxy-diphenyl-dimethyl methane, with the 4,4 isomers predominating and with lesser quantities of the 2,2 and 4,2 isomers being present. It is immaterial which one of these isomers is used and the commercially available mixture is entirely satisfactory.

Attention is again directed to the fact that in the instant part, to wit, Part 1, and in succeeding parts, the text is concerned almost entirely with epoxides in which there is no bridging radical or the bridging radical is derived from an aldehyde or a ketone. It would be immaterial if the divalent linking radical would be derived from the other groups illustrated for the reason that nothing more than mere substitution ofone compound for the other would be required. Thus, what is said hereinafter, although directed to one class or a few classes, applies with equal force and effect to the other classes of epoxide reactants.

If sulfur-containing compounds are prepared they should be freed from impurities with considerable care for the reason that any time that a low-molal sulfurcontaining compound can react with epichlorohydrin there may be formed a by-product in which the chlorine happened to be particularly reactive and may represent a product, or a mixture of products, which would be unusually toxic, even though in comparatively small concentration.

PART 2 Treatment with epichlorohydrin, for example, does not 'yield this product initially but there is an intermediate produced which can be indicated by the following structure:

Treatment with alkali, of course, forms the epoxy ring. A number of problems are involved inattempting to produce this compound free from cogeneric materials of related composition. The difiiculty stems from a number of sources and a few of'the more important ones are as follows:

OH: H H H H H H HC-O [OCC 0%-OOH 0 (I111; (B (in (2) Even if one starts with the reactants in the preferred ratio, to wit, two parts of epichlorohydrin to one part of bis phenol A, they do not necessarily so react and as a result one may obtain products in which more than .two epichlorohydrin residues became attached to a single bis-phenol A nucleus by virtue of the reactive hydroxyls present which enter into oxyalkylation reactions rather than ring closure reactions.

(3) As is well known, ethylene oxide in the presence of alkali, and for that matter in the complete absence of water, forms cyclic polymers. Indeed, ethylene oxide can produce a solid polymer. This same reaction can, and at times apparently does, take place in connection with compounds having one, or in the present instance,

two substituted oxirane rings, i. e., substituted 1,2 epoxy rings. Thus, in many ways it is easier to produce a poly- .mer, particularly a mixture of the monomer, dimer and trimer, than it is to produce the monomer alone. i

(4) As has been pointed out previously, monoepoxldes may be present and, indeed, are almost invariably and inevitably present when one attempts to produce polyepoxides, and particularly diepoxides. The reason is the one which has been indicated previously, together with the fact that in the ordinary course of reaction a diepoxide, such as Q H I H may react with a mole of bis-phenol A to give a monoepoxy structure. Indeed, in the subsequent text immediately following reference is made to the dimers, trimers and tetramers in which two epoxide groups are present. Needless to say, compounds can be formed which correspond in every respect except that one termin the open market.

vherein described soluble materials.

nal epoxide group is absent and in its place is a group having one chlorine atom and one hydroxyl group, or else two hydroxyl groups, or an unreacted phenolic ring.

(5) Some reference has been made to the presence of a chlorine atom and although all effort is directed towards the elimination of any chlorine-containing molecule yet it is apparent-that this isoften an ideal approach rather than a practical possibility. Indeed, the same sort of reactants are sometimes employed to obtain products in which intentionally there is both an epoxide group and a chlorine atom present. See U. S. Patent No. 2,581,464, dated January 8, 1952, to Zech.

What has been said in regard to the theoretical aspect is, of course, closely related to the actual method of preparation which is discussed in greater detail, in Part 3, particularly subdivisions A and B. There can be no clear line between the theoretical aspect and actual preparative steps. However, in order to summarize or illustrate what has been said in Part 1, immediately preceding reference will be made to a typical example which already has been employed for purpose of illustration. The particular example is It is obvious that two moles of such material combine readily with one mole of bis-phenol A,

to produce the product which is one step further along, at least, towards polymerization. In other words, one

prior example shows the reaction product obtained from 'next formula is in essence one which, perhaps in an idealized way, establishes the composition of resinous products available under the name of Epon Resins as now sold See, also, chemical pamphlet entitled Epon Surface-Coating Resins, Shell Chemical CorporatiornNew York city. The word Epon is a registered trademark of the Shell Chemical Corporation.

For the purpose of the instant invention, It may represent a number including zero, and at the most a low number such as 1, 2 or 3. This limitation does not exist in actual efforts to obtain resins as differentiated from the It is quite probable that in the resinous products as marketed for coating use the value of n is usually substantially higher. Note again what has been said previously that any formula is, at best, an over-simplification, or at the most represents perhaps only the more important or principal constituent or constituents. These materials may vary from simple non-resinous to complex resinous epoxides which are compounds having both an epoxy ring or the equivalent 7 and also a hydroxyl group, one need go no further than to in which the various characters have their prior signifi-' consider the reaction product of canoe and in which R is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom and a nu and bisphenol A in a mole-for-rnole ratio, since the initial reactant would yield a product having an unreacted epoxy ring and two reactive hydroxyl radicals. Referring again to a previous formula, consider an example where two 10 moles of bisphenol A have been reacted with 3 moles of in which and represent hydlogeniahd hydro epichlorohydrin, Th simplest compound f m d ld carbon substituents of the aromatic nucleus, said substib th tuent member having not over 18 carbon atoms; n repre- (IJH: ()H JH: (23;, OH; OH: (EH, 0H CH 0 on, a CH1 Such a compound is comparable to other compounds havsents an integer selected from the class of zero and 1, ing both the hydroxyl and epoxy ring such as 9,10-epoxy and n represents a whole number not greater than 3. octadecanol. The ease with which this type of compound PART. polymerizes is pointed out by U. S. Patent No. 2,457,329,, dated December 28, 1948, to Swern et al. I SubdlvlslonA The same difliculty which involves the tendency to poly- The preparations of the diepoxy derivatives of the dimerize on the part of compounds having a reactive ring; phenols, which are sometimes. refierredwto':as-diglycydyl and a hydroxyl radical may be illustrated by compounds ethers, have been. described in a number of patents. For where, instead of the oxirane ring (1,2-epoxy ring) there convenience, reference will be made to two only, to wit, is present a 1,3-epoxy ring. Such compounds are derivaaforementioned U. S. Patent 2,506,486, and aforementives of trimethylene oxide rather than ethylene'oxide. tioned U. S. Patent No. 2,530,353: See U. S. Patents Nos. 2,462,047 and 2,462,048, both Purely by way of illustration, the following diepoxides, dated February 15, 1949, to Wyler. or diglycidyl others as they are sometimes termed, are At the expense of repetition of what appeared previousincluded for purpose of illustration. These particular ly, it may be well to recall that these materials may vary compounds are described in the two patents. just men; from simple soluble non-resinous to complex non-soluble tioned.

TABLE I Exl Patent ample Dlphenol Diglycidyl ether refernumber ence CH c H OH D1 h 1 th 2, 506,486 eH;&H .H. 6H DrE83$35883Bh1$Zthi&ethane.. 506 486 (CH;)C(CH4OH) Dl(epoxypropoxyphenyl)dimethylmethane. CzHlc (CH3) (CQH-IOH) D l(epoxy-propoxyphenyl)ethylmethylmethane (6211910 (CeHiOH) Dl(epoxypropoxyphenyl)dlethyhnethane CH3C(C3H1)(O0H4OH)1. Di(eopxypropoxyphenyl)methyl' ropylmethan C1130 (CqHs) (C6H4OH)L D1(epoxypropoxyphen3 l)methyl henylmethana 2 sC(CaH5)( a 4 a... Di(epoxypropoxyphenyl)ethylphenylmethane. O H7C(OuHs)(CeH4OH)q Di(epoxypropoxyphenyl)propylphen lrnethanav O4HnO(OeHs)(C H OH): Dl(epoxypropoxyphenyl)butylpheny 5 ethane (CH;CH4) CH (O6H4OH) 1.. Di(opoxypropoxyphenyl)tolylmethane (CEbC Hi) C(CHs) (OIHAOH) Dl(epoxypropoxyphenyl)tolylmethylm hane. Dihydroxy diphenyl 4,4 bis(2,3-epoxypropoxy)diphenyl (CH C (O4H5.O@H3OH')'; 2,2-bis t-(2,3-epoxypro'poxy) Z-tertlarybutyI phen'yl) resinous epoxides which are polyether derivatives of poly- Subdivision 3 hydric phenols containing an average of more than one 5.5 epoxide group per molecule and free from functional A8 to the p p' of low-molal Polymeric epoxldes groups other than epoxide and y y groups e or mixtures reference is-made to-numerous patents and tig latter hlghly resmous particularly the. aforementioned U. S. Patents Nos. or 11180 u e es, are no p In summary then in light of what has been said, com- 25751558 and pounds Suitable for reaction with amines may be In light of aforementioned U. S. Patent No. 2,575,558, marized by the following formula: the following examples can be specified by reference to R!!! I I R!!! H I I fill! RI! RI! RI! RI R! R! or for greater simplicity the formula could be restated the formula therein provided one still bears in mind it is thus: in essence an over-simplification.

' TABLE 11 (in which the characters have their previous significance) Example R- 7 n 1: Remarks number r B1 Hydroxy benzene CH 1 0,1, 2 Phenol known as bishenol A. Low I e polymeric mixture a out or more where 'n=0, remainder largely where l n=1, some where n=2. CH:

B2 -.do OH; 1 0, 1, 2 Phenol known as bis-phenol B. See note (13 I regarding B1 above. (EH2 CHa B3 Orthobutylphenol CH 1 0, 1, 2 Even though 11' is preferably 0, yet the usual reaction product might well 0ontain materials where 'n' is 1, or to a I lesser degree 2. r r 1 CH:

2B4 Orthoamylpherlol CH; 1 0,1,2 Do.

B5 Orthooetylphenol CH; 1 0, 1, 2 Do.

v CHI B6 Orthononylphenol ([1131; 1 0,1,2 Do.

' o I CH3 I B7 Orthododecy1phenol (3H3 ,1 0, 1,2 Do.

CHI

B8. Metecresol CH1 1 0, 1, 2 See prior note. This phenol used as I initial material is known as bis-phenol C- C. For other suitable bis-phenols see I U. S. Patent 2,564,191. CH:

139 ..d0 (13H; 1 0, 1, 2 See prior note.

. (l} (63H: CH:

.B10. Dibutyl (ortho-pera). phenol- I 1 1 0, 1, 2 Do.

1311 Diamyl (ortho-pere) phenol. 1g 1 0,1,2 Do.

H 312.-..-. Dioctyl (ortho-pera) phenol- 1(1J 1 0, 1, 2 Do.

1313 Dinonyl (ortho-pare) phone]. 15 1 0, 1, 2 Do.

i I H B14 Diamyl (ortho-pera) phenol. 1g 1 0, 1, 2 Do.

B15 .-do H 1 0,1,2 Do.

Cr s B16 Hydroxy benzene ('3 1 0,1,2 .Do.

Bl7- Diamyl phenol (ortho-para); -S'S- 1 0, 1, 2 Do.

B18 do -S 1 I), 1, 2 Do.

Dibutyl phenol (ortho-pare)- El E0! 1 0, 1,2; Do.

TABLE II (continued) Example R from HR1OH R n Remarks number B Dlbutylphenol(ortho-para). 1% g 1 0,1,2 See priornote.

B21 Dinonylphenol(ortho-para)- 1g 1 0,1,2 D0.

in H

B22 Hydroxy benzene (I? 1 0,1,2 Do.

1323 do None 0 0,1,2 D0.

B24- Orthodsopropyl phenol CH3 1 0,1,2 See prior note. As to preparation of 4,4-

[ isopropylidene bis-(Z-isopropylphenol) C see U. S. Patent No. 2,482,748, dated (g 'Sept 27, 1949, to Dietzler.

B25 Para-octyl phenol CH:SCH2 1 0,1,2 See priornote. (As to preparation ofthe phenol sulfide see U. S. Patent No. 2,488,1.34, dated Nov. 15, 1949, to Mikeska et a1.)

1826..-. Hydroxybenzene CH3 1 0,1,2 See prior note. (As to preparation of-the phenol sulfide see U. S. Paton No. 2,526,545.)

iHz l 0:115

Subdivision C Other samples include: 'OH OH H l The prior examples have been limited largely to those I R in which there is no divalent linking radical, as in the 40 1 case of diphenyl compounds, or where the linking radi- R1 cal is derived from a ketone or aldehyde, particularly a ketone. Needless to say, the same procedure is em- CH3 CH3 ployed m convertmg diphenyl mto a dlglycidyl ether regardless of the nature of the bond between the two wherein .R1 18 a substltuent'selected from the class connolic nuclei. For purpose of illustration attention is directed to numerous other diphenols which can be readily converted to a suitable polyepoxide, and particularly diepoxide, reactant.

As previously pointed out the initial phenol may be substituted, and the substituent group in turn may be a cyclic group such as the phenyl group or cyclohexyl group as in the instance of cyclohexylphenol or phenylphenol. Such substituents are usually in the ortho position and may be illustrated by a phenol of the following composition:

Similar phenols which are monofunctional, for instance, paraphenyl phenol or paracyclohexyl phenol with an additional substituent in the ortho position, may be employed in reactions previously referred to, for instance, with formaldehyde or sulfur chlorides to give comparable phenolic compounds having 2 hydroxyls and suitable for subsequent reaction with epichlorohydrin, etc.

sisting of secondary butyl and tertiary butyl groups and R2 is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups, and wherein said alkyl group contains at least 3 carbon atoms. See U. S. Patent No. 2,515,907.

CsHn 051111 in which the C5H11 groups are secondary amyl groups. See U. S. Patent No. 2,504,064.

See U. S. Patent N0. 2,285,563.

H on: H om OHr-O-OH;

' 15 See U. s. Patent No. 2,503,196.

wherein R is a member of the group consisting of alkyl, and alkoxyalkyl radicals containing from 1 to carbon atoms, inclusive, and aryl and chloraryl radicals of the benzene series. See U. S. Patent No. 2,526,545.

OH OH 1 (i3 x R:

CH: OH;

wherein R1 is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R2 is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups. See U. S. Patent No. 2,515,906.

HIO'O OH| H:COOH:

C 1Hs (3H3 See U. S. Patent No. 2,515,908.

As to sulfides, the folowing compound is of interest:

05H Cs u See U. S. Patent No. 2,331,448.

As to descriptions of various suitable phenol sulfides, reference is made to the following patents: U. S. Patents Nos. 2,246,321, 2,207,719, 2,174,248, 2,139,766, 2,244,021, and 2,195,539.

As to sulfones, see U. S. Patent No. 2,122,958.

As to suitable compounds obtained by the use of formaldehyde or some other aldehyde, particularly compounds such as H H O 0 B Alkyl Alkyl Alkyl fides, the disulfides, and the polysulfides. The following formula represents the various dicresol sulfides of this invention:

OH 0H. on. on

R: R1 R1 R1 in which R1 and R2 are alkyl groups, the sum of whose di(dialkyl cresol) sulfides which include the monosul- 16 carbon atoms equals 6 to about 20, and R1 and R2 each preferably contain 3 to about 10 carbon atoms, and x is 1 to 4. The term sulfides as used in this text, therefore, includes monosulfide, disulfide, and polysulfides.

PART 4 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble,

Water-insoluble resin polymers of a composition approximated in an idealized form by the formula OH OH OH H r .1 [TO R R n R 1 In the above formula n represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably 10-or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, Le, n varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 15 carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resins are derived from trifunctional phenols as previously noted. However, even when obtained from a difunctional phenol, for instance paraphenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such as benzene, or xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or diethyleneglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and non-oxygenated) will serve. See Example 9a of US. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as, described in aforementioned US. Patent No. 2,499,365, or in US Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. In said patent there are described oxyalkylation-susceptible, fusible, nonoxygenated-organic solvent-soluble, water-insoluble, lowstage phenol-aldehyde resins having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule. These resins are difunctional only in regard to methylol-forming reactivity, are dervied by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol and are formed in the substantial absence of trifunctional phenols. The phenol is of the formula with two moles of formaldehyde and two moles of a basic nonhydroxylated secondary amine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated The basic nonhydroxylated amine may be designed thus:

In conducting reactions of this kind one does not necessarily obtain a hundred per cent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde, or only one mole of the amine may combine with the resin molecule, or even to a very slight extent, if at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas:

As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified R R R in which R' is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst, having neither acid nor basic properties in the ordinary sense or Without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of of a percent and as much as a few IOths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In the preparing resins one does not get a single poly- 1 8 mer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins we found no reason for using other than those which are lowest in price and most readily available commercially. For purposes of convenience suitable resins are characterized in the following table:

TABLE III M01. wt.

Ex- R of resin ample R Position derived n molecule number of R from- (based on n+2) Phe'uyl 3.5 992. 5

Tertiary butyl 3. 5 882. 5 Secondary butyL. 3.5 882. 5 Cyelo-hexyl 8. 5 1,025. 5 Tertiary amyl 3. 5 959. 5 Mixed secondary 3. 5 805. 5

and tertiary amyl.

Propyl 3. 5 805. 5 Tertiary hexyl. 3. 5 1, 036. 5 Octyl 3. 5 1, 190. 5 NonyL. 3. 5 l, 267. 5 Decyl 3. 5 1, 344. 5 Dodecyl 3. 5 1, 498. 5 Tertiary butyl 3. 5 945. 5

Tertiary amyl 3. 5 1,022.5 Nonyl 3. 5 1. 330. 5 Tertiary butyl 3. 5 1,071.5

Tertiary amyl 3. 5 1, 148. 5 Nonyl d 3. 5 1, 456. 5

Tertiary buty1 .do..... Proplon- Tertiary amyl 3. 5 1, 085. 5 ony 3.5 1,393.5 Tertiary butyl 4. 2 996. 6

Tertiary amyl 4. 2 1, 083. 4 Nonyl 4. 2 1. 430. 6 Tertiary butyl- 4v 8 1, 094.4 Tertiary amyL. 4. 8 1, 189. 6 Nonyl 4. 8 1, 570. 4 Tertiary amyL. 1. 5 (104.0 Oyclo-hexyl. 1. 5 646. 0 H 1. 5 653. 0 1. 5 688. 0

Hexyl 2.0 748. 0 Cyc1o-hexyl- 2.0 740. 0

PART 5 As has been pointed out, the amine herein employed as a reactant is a basic secondary polyamine and preferably a strongly basic secondary polyamine free from hydroxyl groups, free from primary amino groups, free from substituted imidazoline groups, and free from substituted tetrahydropyrimidine groups, in which the hydrocarbon radicals present, whether monovalent or divalent are alkyl, alicyclic, arylalkyl, or heterocyclic in character.

Previous reference has been made to a number of polyamines which are satisfactory for use as reactants in the instant condensation procedure. The cheapest amines available are polyethylene amines and polypropylene amines. In the case of the polyethylene amines there may be as many as 5, 6 or 7 nitrogen atoms. Such amines are susceptible to terminal alkylation or the equivalent, i. e., reactions which convert the terminal primary amino group or groups into a secondary or tertiary amine radical. In the case of polyamines having at least 3 nitrogen atoms or more, both terminal groups could be converted into tertiary groups, or one terminal group could be converted into a tertiary group and the other into a secondary amino group. By way of example the fol- 19 lowing formulas are included. It will be noted they include some polyamines which, instead of being obtained rom dichloride, propylene dichloride, or the like, are obtained from dichloroethyl ethers in which the divalent radical has a carbon atom chain interrupted by an oxygen atom:

CH3 CH3 Another procedure for producing suitable polyamines is a reaction involving first an alkylene imine, such as ethylene imine or propylene imine, followed by an alkylating agent of the kind described, for example, dimethylsulfate; or else a reaction which involves an alkylene oxide, such as ethylene oxide or propylene oxide, followed by the use of an alkylating agent or the comparable procedure in which a halide is used.

What has been said previously may be illustrated by reactions involving a secondary alkyl amine, or a secondary aralkyl amine, or a secondary alicyclic amine, such as dibutylamine, dibenzylamine, dicyclohexylamine, or mixed amines with an imine so as to introduce a primary amino group which can be reacted with an alkylating agent, such as dimethyl sulfate. In a somewhat similar procedure the secondary amine of the kind just specified can be reacted with an alkylene oxide such as ethylene oxide, propylene oxide, or the like, and then reacted with an irnine followed by the final step noted above in order to convert the primary amino group into a secondary amino group.

Reactions involving the same two classes of reactants previously described, i. e., a secondary amine plus an imine plus an alkylating agent, or a secondary amine plus an alkylene oxide plus an imine plus an alkylating agent, can be applied to another class of primary amines which are particularly desirable for the reason that they introduce a definite hydrophile effect by virtue of an ether linkage, or repetitious ether linkage, are certain basic polyether amines of the formula:

20 with the proviso that'the sum of m plus m equals 2; and R has its prior significance, particularly as a hydrocarbon radical. I

Monoamines so obtained and suitable for conversion into appropriate polyamines are exemplified by Other somewhat similar secondary monoamines equally suitable for such conversion reactions in order to yield appropriate secondary amines, are those of the composition R0(oH'2)i as described in U. S. Patent No. 2,375,659, dated May 8, 1945, to Jones et al. In the above formula R may be methyl, ethyl, propyl, amyl, octyl, etc.

Other suitable secondary amines which can be converted into appropriate polyamines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylrnethylamine or the alkylation of similar primary amines, or for that matter, amines of the kind described in U. S. Patent No. 2,482,546, dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta phenoxyethylamine, gamma phenoxypropylamine, beta-phenoxy-alpha-methylethylamine, and beta-phenoxypropylamine. 1

Other secondary monoamines suitable for conversion into polyamines are the kind described in British Patent No. 456,517 and may be illustrated by In light of the various examples of polyamines which have been used for illustration it may be well to refer again to the fact that previously the amine was shown with the statement that such presentation is an oversimplification. It was pointed out that at least one occurrence of R must include a secondary amino radical of the kind specified. Actually, if the polyamine radical contains two or more secondary amino groups the amine may react to two different positions and thus the same amine may yield compounds in which R and R are dissimilar. examples:

CH3 CH3 H N propylene N propylene N In the first of the two above formulas if the reaction involves a terminal amino hydrogen obviously the radicals attached to the nitrogen atom, which in turn combines with the methylene bridge, would be different than if the reaction took place at the intermediate secondary amino radical as differentiated from the terminal group. Again, referring to the second formula above, although a terminal amino radical is not involved it is obvious again that one could obtain two different structures for the radicals attached to the nitrogen atom united to the methylene bridge, depending whether the reaction took place at either one of the two outer secondary amino groups, or at the central secondary amino group. If there are two points of reactivity towards formaldehyde as illustrated by the'above examples it is obvious that one might get a mixture in which in part the reaction took This is illustrated by reference to two prior Over and above the specific examples which have appeared previously, attention is directed to the fact that added suitable polyamines are shown in subsequent Table IV.

PART 6 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difiicult to actually depict the final product of the cogeneric mixture except in terms of the process itself.

Previous reference has been made to the fact that the procedure herein employed is comparable, in a general way, to that which corresponds to somewhat similar derivatives made either from phenols as differentiated from a resin, or in the manufacture of a phenol-amine-aldehyde resin; or else from a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557 in order to obtain a heatreactive resin. Since the condensation products obtained are not heat-convertible and since manufacture is not restricted to a single phase system, and since temperatures up to 150 C. or thereabouts may be employed, it is obvious that the procedure becomes comparatively simple. Indeed, perhaps no description is necessary over and above what has been said previously, in light of subsequent examples. However, for purpose of clarity he following details are included.

A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher temperatures, for instance, ordinary room temperature. Thus, we have found it convenient to use a solvent and particu larly one which can be removed readily at a comparatively moderate temperature, for instance, at 150 C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively non-volatile solvent such as dioxane or the diethylether of ethylene glycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only in an oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction.

Actually, water is apt to be present as a solvent for the reason that in most cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 37%, or it may be diluted down to about 30% formaldehyde. However, paraformaldehyde can be used but it is more 'diflicult perhaps to add a solid material instead of the liquid solution, and, everything else being equal, the latter is apt to be more economical. In any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction. However, if the reaction mass is going to be subjected to some further reaction where the solvent may be objectionable, as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxyalkylation, then, obviously, the alcohol should not be used or else it should be removed. The fact that an oxygenated solvent need not be employed, of course, is an advantage for reasons stated.

Another factor, as far as the selection of solvent goes, is whether or not the cogeneric mixture obtained at the end of the reaction is to be used as such or in the salt form. The cogeneric mixtures obtained are apt to be solids or thick viscous liquids in which there is some change from the initial resin itself, particularly if some of the initial solvent is apt to remain without complete removal. Even if one starts with a resin which is almost water-white in color, the products obtained are almost invariably a dark red in color or at least a redamber, or some color which includes both an amber component and a reddish component. By and large, the melting point is apt to be lower and the products may be more sticky and more tacky than the original resin itself. Depending on the resin selected and on the amine selected the condensation product or reaction mass on a solvent-free basis may be hard, resinous and comparable to the resin itself.

The products obtained, depending on the reactants selected, may be water-insoluble or water-dispersible, or water-soluble, or close to being water-soluble. Watersolubility in enhanced, of course, by making a solution in the acidified vehicles such as a dilute solution, for instance, a 5% solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc. One also may convert the finished product into salts by simply adding a stoichicmetric amount of any selected acid and removing any. water present by refluxing with benzene or the like. In fact, the selection of the solvent employed may depend in part whether or not the product at the completion of the reaction is to be converted into a salt form.

In the next succeeding paragraph it is pointed out that frequently it is convenient to eliminate all solvent, using a temperature of not over C. and employing vacuum, if required. This applies, of course, only to those circumstances where it is desirable or necessary to remove the solvent. Petroleum solvents, aromatic solvents, etc., can be used. The selection of solvent, such as benzene, xylene, or the like, depends primarily on cost, i. e., the use of the most economical solvent and also on three other factors, two of which have been previously mentioned; (a) is the solvent to remain in the reaction mass without removal? (/1) is the reaction mass to be subjected to further reaction in which the solvent, for instance, an alcohol, either low boiling or high boiling, might interfere as in the case of oxyalkylation? and the third factor is this, (8) is an effort to be made to purify the reaction mass by the usual procedure as, for example, a water-wash to remove the water-soluble unreacted formaldehyde, if any, or a water-wash to remove any unreacted water-soluble poly-amine, if employed and present after reaction? Such procedures are well known and, needless to say, certain solvents are more suitable than others. Everything else being equal, we have found xylene the most satisfactory solvent.

We have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure. There is no objection, of course, to giving the reaction an opportunity to proceed as far as it will at some low temperature, for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. I have not found any case where it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, we are not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be [conducted at a lower temperature so as to use up part of the formaldehyde at such lower temperature, then the amount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but may be convenient under certain circumstances. On the other hand, if the products are not mutually soluble then agitation should be more vigorous for the reason that reaction probably takes place principally at the interfaces and the more vigorous the agitation the more interfacial area. The general procedure employed is invariably the same when adding the resin and the selected solvent, such as benzene or xylene. Refluxing should be long enough to insure that the resin added, preferably in a powdered form, is completely soluble. However, if the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned U. S. Patent 2,499,368. After the resin is in complete solution the polyamine is added and stirred. Depending on the polyamine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible that the initial reaction mass could be a three-phase system instead of a two-phase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example 35 C. or slightly lower, provided this initial low temperature stage is employed. The formaldehyde is then added in a suitable form. For reasons pointed out we prefer to use a solution and whether to use a commercial 37% concentration is simply a matter of choice. In large scale manufacturing there may be some advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction has proceeded as one can reasonably expect at a low temperature, for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C. for 4 or 5 hours, or at the most, up to -24 hours, we then complete the reaction by raising the temperature up to 150 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of polyamine or formaldehyde. At a higher temperature we use a phase-separating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. We then permit the temperature to rise to somewhere about 100 C., and generally slightly above C. and below C. by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is eliminated, is continued until the reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same way as the removal of solvents in resin manufacture as described in aforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary polyamine and 2 moles of formaldehyde. In some instances we have added a trace of caustic as an added catalyst but have found no particular advantage in this. In other cases we have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In other cases we have used a slight excess of amine and, again, have not found any particular advantage in so doing. Whenever feasible we have checked the completeness of reaction in the usual ways, including the amount of water of reaction, molecular Weight, and particularly in some instances have checked whether or not the end-product showed surface-activity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted polyamine, if any is present, is another index.

In light of what has been said previously, little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration:

Example 1b The phenol-aldehyde resin is the one that has been identified previously as Example 2a. It was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei, as the value for n which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams ofthe resin identified as 2a preceding were powdered and mixed with a somewhat lesser weight of xylene, i. e., 600 grams. The mixture was refluxed until solution was complete. It was .then adjusted to approximately 30 to 35 C. and 176 grams of symmetrical dimethyl-ethylene diamine added. The mixture was stirred vigorously and formaldehyde added slowly. In this particular instance the formaldehyde used was a 30% solution and 200 grams were employed which were added in a little short of 3 hours. The mixture was stirred vigorously and kept within a temperature range of 30 to 46 for about 19 hours. At the end of this time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time. The presence of unreacted formaldehyde was noted. Any unreacted formaldehyde seemed to disappear within approximately two to three hours after refluxing started. As soon as the odor of formaldehyde was no longer detectible the phase-separating trap was set so as to eliminate all the water of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached approximately 152 C., or slightly higher. The mass was kept at this higher temperature for three to four hours and reaction stopped. During this time, any additional water which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene and the residual material was dark red in color and had the consistency of a sticky fluid or tacky resin. The over- 11 H all time for reaction was somewhat less than 30 hours. A b v In other examples, it varied from a little over 20 hours iup to 36 hours. The time can be reduced by cutting the OH; OH, low temperature period to approximately 3 to 6 hours.

Note that in Table IV following there are a large num- H2 H2 ber of added examples illustrating the same procedure. 0-

In each case the initial nnxt lre was stirred and held at Amine 0 NCHNOH a fairly low temperature (30 to 40 C.) for a period of H several hours. Then refluxing was employed until the 10 gy odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both the solution H and condensation. After all the water had been sep- Amine 0,3,)mHONQmCmCmN/ arated enough xylene was taken out to have the final CH product reflux for several hours somewhere in the range of 145 to 150 C., or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the 011K /0H= water, or all of the water, had been removed Amine NCZHNCzHNClHN Note that as pointed out prevlously, this procedure 18 20 H H illustrated by 24 examples in Table IV. H H

TABLE IV Strength of Reac- Reac- Max. Ex Resin Amt, Amine used and amount formal- Solvent used tiOl'l tiOll distill. No. used grs. dehyde 50111. and amt. temn, time temp,

and amt. 0. (hrs) C.

882 Amine A, 176g 200 g.-- Xylene, 600g... 20-23 26 152 32% r 88 tit 22 s n o y ene, g 5 441 Amine B, 116 g. 37%, 81 g Xylene, 400 g. 20-28 36 144 as s2 212:2 s8:-

12s O a 882 Amine G, 204 g. 30%, 200 g.-. do 21-23 30 145 480 Amine O, 102 g 37%,100 Xylene, 450 g..- 20-25 14s d Xylene, 5001;" 20-27 35 143 do Xylene, 425 g 20-22 31 145 "do Xylene, 500 21-26 24 146 do 22-25 36 151 e an: a lit 0 0 do Xylene, 550 21-26 27 145 30%, 100g Xylene, 400 g.-. 20-23 25 141 do do 22-27 29 143 do Xylene, 450 g. 23-25 36 149 do do 21-26 32 148 do Xylene, 500 g... 21-23 30 148 o y ene, g Amine H, 282 g- 37%, 81 g Xylene, 500 21-28 25 150 391 AmineH, 141 30%,50g.- Xylene, 350 g... 21-22 28 151 As to the formulas of the above amines referred to Amine H as Amine A through Amine H, inclusive, see immedi- CHPOH: CHZCH ately below:

CH30C HCNH-C2H4NHCL HO-OCH:

CHa-CHz onion, Amine 11- NCgHAN PA on. on. RT 7 H H The products obtained as herein described by reaction A B H involving amine condensates and diglycidyl ethers or the mm t 2 equivalent are valuable for use as such. This is pointed CzHs Cz s out in detail elsewhere. However, in many instances the derivatives obtained by oxyalkylation are even more 22s to t1: 1iiormutlas o f fill?! 1"? gf' valuable and from such standpoint the herein described t mug Amme uslve See e y products may be considered as valuable intermediates. Subsequent oxyalkylation involves the use of ethylene H H 05 oxide, propylene oxide, butylene oxide, glyc-ide, etc. Such oxyalkylating agents are monoepoxides as differen- Amme NOZHN tiated from polyepoxides.

CH; CH: It becomes apparent that if the product obtained is to H H be treated subsequently with a m'onoepoxide which may require a pressure vessel as in the case of ethylene oxide, Amine B- N 02 1 it is convenient to use the same reaction vessel in both E instances. In other words, the 2 moles of the amine- CzHs C: s

modified phenol-aldehyde resin condensate would be Ame H reacted with a polyepoxide and then subsequently with a NCsHoN m'onoepoxide. In any event, if desired the polyepoxide reaction can be conducted in an ordinary reaction vessel,

27 such as the usual glass laboratory equipment. This is particularly true of the kind used for resin manufacture as described in a number of patents, as for example, U. S. Patent No. 2,499,365.

Cognizance should be taken of one particular feature in connection with the reaction involving the polyepoxide and that is this; the amine-modified phenol-aldehyde resin condensate is invariably basic and thus one need not add the usual catalysts which are used to promote such reactions. Generally speaking, the reaction will proceed at a satisfactory rate under suitable conditions without any catalyst at all.

Employing polyepoxides in combination with a nonbasic reactant the usual catalysts include alkaline materials such as caustic soda, caustic potash, sodium methylate, etc. Other catalysts may be acidic in nature and are of the kind characterized by iron and tin chloride. Furthermore, insoluble catalysts such as clays or specially prepared mineral catalysts have been used. If for any reason the reaction did not proceed rapidly enough with the diglycidyl ether or other analogous reactant, then a small amount of finely divided caustic soda or sodium methylate could be employed as a catalyst. The amount generally employed would be 1% or 2%.

It goes without saying that the reaction can take place in an inert solvent, i. e., 'one that is not oxyalkylationsusceptible. Generally speaking, this is most conveniently an aromatic solvent such as xylene or a higher boiling coal tar solvent, or else a similar high boiling aromatic solvent obtained from petroleum. One can employ an oxygenated solvent such as the diethylether of ethylene glycol, or the diethylether of propylene glycol, or similar ethers, either alone or in combination with a hydrocarbon solvent. The selection of the solvent depends in part on the subsequent use of the derivatives or reaction products. If the reaction products are to be rendered solvent-free and it is necessary that the solvent be readily removed as, for example, by the use of vacuum distillation, thus xylene or an aromatic petroleum will serve. If the product is going to be subjected to oxyalkylation subsequently, then the solvent should be one which is not oxyalkylation-susceptible. It is easy enough to select a suitable solvent if required in any instance but, everything else being equal, the solvent chosen should be the most economical one.

Example 1C The product was obtained by reaction between the diepoxide previously designated as diepoxide 3A, and condensate 2b. Condensate 2b was obtained from resin 5a. Resin 5a was obtained from tertiary amylphenol and formaldehyde. Condensate 2b employed as reactants resin 5a and the amine designated as Amine A at the end of Table IV which is symmetrical dimethyl ethylene- 28 diam'ine'. The amount of resin employed was 882 grams; the amount :of symmetrical dimethyl ethylenediamine employed was 176 gramsyand the amount of 30% formaldehyde employed was 200 grams. The amount of solvent was approximately 600 grams. All this has been described previously.

The solution of the condensate in xylene was adjusted to a solution. In this particular instance, and in practically all the others which appear in a subsequent table, the examples are characterized by the fact that no alkaline catalyst was added. The reason is, of course, that the condensate as such is strongly basic. If desired, a small amount of an alkaline catalyst could be added, such asfinelypowdered caustic soda, sodium methylate, etc. If such alkaline catalyst is added it may speed up the reaction but it also may cause an undesirable reaction, such as the polymerization of a diepoxide.

In any event, 116 grams of the condensate dissolved in approximately 116 grams of xylene were stirred and heated to C. .17 grams of the diepoxide previously identified as 3A and dissolved in an equal weight of xylene were added dropwise. An initial addition of the xylene solution carried the temperature to 109 C. The remainder of diepoxide was added in approximately one hours time. During this period the temperature rose to about 118 C. The product was allowed to reflux at a temperature of about 128 C. using a phase-separating trap. A small amount of xylene was removed by means of the phase-separating trap so the refluxing temperature rose to a maximum of 160 C. The mixture was then refluxed at 160 C. for about 6 hours until the reaction stopped and the xylene which had been removed during the refiux period was returned to the mixture. A small amount of material was withdrawn and the xylene evaporated on the hot plate in order to examine the physical properties. The material was a dark red viscous semisolid. It was insoluble in water, it was insoluble in 5% gluconic acid, and it was soluble in xylene, and particularly in a mixture of 80% xylene and 20% methanol. However, if the material was dissolved in an oxygenated solvent and then shaken with 5% gluconic acid it showed a definite tendency to disperse, suspend, or form a sol, and particularly in a xylene-methanol mixed solvent as previously described, with or without the further addition of a little acetone.

1 The procedure employed of course is simple in light of what has been said previously and in effect is a procedure similar to that employed in the use of glycide or methylglycide as oxyalkylating agents. See, for example, Part 1 of U. S. Patent No. 2,602,062 dated July 1, 1952, to De Groote.

Various examples obtained in substantially the same manner are enumerated in the following tables:

TABLE V Con- Diep- Time Max. Ex den- Amt, oxide Amt, Xylene, Molar of reactemp Color and physical st ate No sate grs. used grs. grs. ratio tion, 0. used hrs. 7

116 3A 17 133 2:1 6 160 Dark semi-solid. 122 3A 17 139 2:1 7 165 Do. 111 3A 17 128 2:1 6 162 D0. 119 3A "17 136 2:1 6 170 D0. 1A 17 137 2:1 6 Do. 159 3A 17 176 2:1 8 168 Dark solid mass. 122 3A 17 139 2:1 7 Do. 143 3A 17 160 2:1 8 Do. 140 3A 17 157 2:1 8 162 Do. 146 3A 17 163 2:1 8 165 Do.

TABLE VI Oon- Diep- Time Max. Ex. den- Amt, oxide Amt., Xylene, Molar oi reac- -temp., Color and physical state No. sate grs. used grs. grs. ratio tion, C.

used hrs.

1D 21? 116 B1 27. 143. 5 2:1 7 162 Dark semi-solid. 2D 50 122 B1 27.5 149.5 2:1 6 165 Do. 3D. 71) 111 B1 27.5 138.5 2:1 7 160 Do. 4D 81) 119 B1 27. 5 146. 5 2:1 8 165 D0. 5D 120 B1 27. 5 147. 5 2:1 8 168 Do. 6D 12b 159 131 27.5 186. 5 2:1 8 160 Dark solid mass. 7D 13!) 122 B1 27. 5 149. 5 2:1 7 160 Do. 8D 18b 143 B1 27.5 170. 5 2:1 8 162 D0. 9D 1917 140 B1 27.5 167. 5 2:1 8 160 D0. 10D 146 B1 27.5 173. 5 2:1 8 165 D0.

Solubility in regard to all these compounds was substantially similar to that which was described in Example 10.

TABLE VII Probable Resin con- Probable Amt. of Amt. of number of Ex. No. densate mol. wt. of product, solvent, hydroxyls used reaction grs. grs. per moleproduot cule TABLE VIII Probable Resin con- Probable Amt. of Amt. of number ot- Ex. No. densate mol. wt. of product, solvent, hydroxyls used reaction grs. grs. per moleproduct mile 2, 870 2, 870 1, 435 11 2,980 2, 980 1, 490 11 2, 770 2, 770 1, 385 11 2, 926 2, 930 1, 467 11 2, 958 2, 960 1, 481 11 3, 726 3, 730 1,867 11 2, 994 2, 990 l, 493 11 3, 406 3, 400 l, 697 11 3, 354 3,360 l, 683 12 3, 462 3, 460 1, 729 ,12

At times we have found a tendency for an insoluble mass to form or at least to obtain incipient cross-linking or gelling even when the molal ratio is in the order of 2 moles of resin to one of diepoxide. We have found this can be avoided by any one of the following procedures or their equivalent. Dilute the resin or the diepoxide, or both, With an inert solvent, such as xylene or the like. In some instances an oxygenated solvent, such as the diethyl ether of ethyleneglyco'l may be employed. Another procedure which is helpful is to reduce the amount of catalyst used, or reduce the temperature of reaction by adding a small amount of initially lower boiling solvent such as benzene, or use benzene entirely. Also, we have found it desirable at times to use slightly less than apparently the theoretical amount of diepoxide, for instance, 90% to 95% instead of 100%. The reason for this fact may reside in the possibility that the molecular weight dimensions on either the resin molecule or the diepoxide molecule may actually vary from the true molecular weight by several per cent.

Previously the condensate has been depicted in a simplified form which, for convenience, may be shown thus:

(Amine)CHg(Resiri)CHg(A1nine) Following such simplification the reaction product with a polyepoxide and particularly a diepoxide, would be indicated thus:

in which D. G. E. represents a dlglycidyl ether as specified. If the amine happened to have more than one reactive hydrogen, as in the case of a hydroxylated amine or polyamine, having a multiplicity of secondary amino groups it is obvious that other side reactions could take place as indicated by the following formulas:

[(Amine) CHz(Amine)] [D. G.E

[(Amine) OHnAminefl [(Resin)OH2(Resin)] [D G.E

[(Amine)CH2 (Amine)] [(Resin)] All the above indicates the complexity of the reac tion product obtained after treating the amine-modified resin condensate with a polyepoxide and particularly diepoxide as herein described.

PART 8 The preparation of the compounds or products described in Part 7, preceding, involves an oxyalkylating agent, to wit, a polyepoxide and usually a diepoxide. The procedure described in the present part is a further oxyalkylation step but involves the use of a monoepoxide or the equivalent. The principal difference is only that while polyepoxides are invariably nonvolatile and can be reacted under a condenser, at least numerous monoepoxides and particularly ethylene oxide, propylene oxide, butylene oxide, etc., involve somewhat different operating conditions. Glycide and methylglycide react under practically the same conditions as the polyepoxides. Actually, for purpose of convenience, it is most desirable to conduct the previous reaction, 1. e., the one involving the polyepoxide, in equipment such that subsequent reaction with monoepoxides may follow without interruption. In the oxyalkylations carried out to produce compositions used in accordance with the present application, conventional equipment, i. e., a stainless steel autoclave suitably equipped, and conventional oxyalkylation conditions were used.

The amount of monoepoxides employed may be as high as 50 parts of monoepoxide for one part of the polyepoxide treated amine-modified phenol-aldehyde condensation product.

Example 1E The polyepoxide-derived oxyalkylation-susceptible compound employed is the one previously designated and described as Example 1D. Polyepoxide-derived condensate ID was obtained, in turn, from condensate 2b and diepoxide B1. Reference to Table IV shows the composition of condensate 2b. Table IV shows it was obtained from Resin 5a, Amine A and formaldehyde. Amine A is symmetrical dimethyl ethylene diamine. Table 111 shows that Resin 5a was obtained from parasubstituted tertiary amylphenol and formaldehyde.

For purpose of convenience, reference herein and in the tables to the oxyalkylation-susceptible compound will be abbreviated in the table heading as OSC; reference is to the solvent-free material since, for convenience, the amount of solvent is noted in a second column. Actually, part of the solvent may have been present and in practically every case was present in either the resinification process or the condensation process, or in treatment with a polyepoxide. In any event, the amount of solvent present at the time of treatment with a monoepoxide is indicated as a separate item. To be consistent, of course, the oxyalkylation-susceptible compound abbreviated as OSC is indicated on a solventfree basis.

14.35 pounds of the polyepoxide-derived condensate were mixed with 14.35 pounds of solvent (xylene in this series) along with one pound of finely powdered caustic soda as a catalyst. This reaction mixture was treated with 14.25 pounds of ethylene oxide. At the end of the reaction period the molal ratio of oxide to initial compound was approximately 65.0 and the theoretical molecular weight was approximately 5,700.

Adjustment was made in the autoclave to operate at a temperature of 125 to 130 C., and at a pressure of to pounds per square inch.

The time regulator was set so as to inject the ethylene oxide in approximately one-half hour and then continued stirring for hour longer simply as a precaution to insure complete reaction. The reaction went readily and, as a matter of fact, the ethylene oxide could have been injected in probably 30 minutes instead of hour and the subsequent time allowed to insure completion of reaction may have been entirely unnecessary. The speed of reaction, particularly at the low pressure, undoubtedly was due in a large measure to the excellent agitation and also to the comparatively high concentration of catalyst.

The amount of ethylene oxide introduced, as previously a noted, was 14.25 pounds.

A comparatively small sample, less than 50 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned, and also for the purpose of making some tests on various oil field emulsions. The amount withdrawn was so small that no cognizance of this fact is included in the data or subsequent data, or in data reported in tabular form in subsequent Tables IX, X and XI.

The size of the autoclave employed was 35 gallons. In innumerableoxyalkylations we have withdrawn a substantial portion at the end of each step and continued oxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and subjected to oxyalkylation with a ditferent oxide.

Example 2E This example simply illustrates further oxyalkylation of Example 1E, preceding. The oxyalkylation-susceptible compound, to wit, Example 1D, is the same one as was used in Example 1E, preceding, because it is merely a continuation. In the subsequent tables, such as Table 1X, the oxyalkylation-susceptible compound in the horizontal line concerned with Example 2E refers to oxyalkylationsusceptible compound, Example 1D. Actually, one could refer just as properly to Example 1E at this stage. It is immaterial which designation is used so long as it is understood and such practice is used consistently throughout the tables. subsequent steps was less than in the initial stage. The amount introduced in the second step was 4.75 pounds. This means the amount of oxide at the end was 19.0 pounds. It is meant that the ratio of oxide to oxyalkylation-susceptible compound (molar basis) at the end was 96 to' 1. The theoretical molecular weight was almost 6,650. There was no added solvent. In other words, it'remained the same, that is, 14.35 pounds, and there was no added catalyst. The entire procedure was substantially the same as in Example 1E, preceding.

The amount of oxide introduced in the oxyalkylation-su'sceptible compound was 195 to 1.

32 In all succeeding examples the time and pressure were the same aspreviously, to wit, to C., and the pressure 10 to 15 pounds. The time element was hour, the same as before.

Example 3E The oxyethylation proceeded in the same manner as described in Examples 1E and 2E. There was no added solvent and no added catalyst. The oxide added was 4.75 pounds. The total oxide at the end of the oxyalkylation procedure was 23.75 pounds. The molal ratio of oxide to condensate was 128 to 1. The theoretical molecular weight was approximately 7.620. As previously noted, conditions in regard to temperature and pressure were the same as in Examples 1E and 2E. The time period was one hour.

Example 4E The oxyethylation was continued and the amount of oxide added was the same as before, to wit, 4.75 pounds. The amountof oxide added at the end of the reaction was 28.50 pounds. There was no added solvent and no added catalyst. Conditions as far as temperature and pressure are concerned were the same as in previous examples. The time period was the same as before, to wit, one hour. tendency to slow up. The molal ratio of oxide to oxyalkylation-susceptible compound was about to 1 and the theoretical molecular weight was 8,600.

Example 5E The oxy-alkylation was continued with the introduction of another 9.50 pounds of oxide. No added solvent was introduced, and likewise no added catalyst was introduced. The theoretical molecular weight at the end of the reaction was approximately 10,500. The molal ratio of oxide to The time period was 1 /2 hours.

Example 6E The same procedure was followed as in the previous examples without addition of either more catalyst or more solvent. The amount of oxide added was the same as before, to wit, 19.00 pounds. The time required to complete the reaction was two hours. At the end of the reaction the ratio of oxide to oxyalkylation-susceptible compound was approximately 320 to 1, and the theoretical molecular weight was about 14,250.

The same procedure as described in the previous examples was employed in connection with a number of the other condensations described previously. All these data have been presented in tabular form in Tables IX through XIV, inclusive.

In substantially every case a 35-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a lS-gall-on autoclave and then transferred to a ZS-gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finally powdered caustic soda.

Referring now to Tables IX, X and XI, it will be noted thatcompounds 1E through 18E were obtained by the use of ethylene oxide, whereas Examples 19E through 36E were obtained by the use of propylene oxide; and Examples 37E through 54E were obtained by the use of butylene oxide.

Referring now to Table X specifically, it will be noted that the series of examples beginning with 1F were obtained, in turn, by use of both ethylene and propylene oxides, using ethylene first; in fact, using Example 1E as the oxyalkylation-susceptible compound in the first six examples. This applies to series 1F through 18F.

Similarly, series 19F through 36F involve the use of both propylene oxide and ethylene oxide in which the propylene oxide was used first, to wit, 19F was prepared from 2313, a compound which was initially derived by use of propylene oxide.

The reaction at this point showed some v oxide.

Series 73F through 90F involve the use of propylene oxide and butylene oxide, butylene oxide being used first and propylene oxide being used next.

In series 16 through 18G the three oxides were used. It will be noted in Example 1G the initial compound was 76F; Example 76F, in turn, was obtained from a compound in which butylene oxide was used initially and then propylene oxide. Thus, the oxide added in the series 1G through 6G was by use of ethylene oxide as indicated in Table XI.

Referring to Table XI, in regard to Example 196 it will be noted again that the three oxides were used and 196 was obtained from 8F. Example 58F, in turn, was obtained by using butylene oxide first and then ethylene oxide. In Example 19G and subsequent examples, such as 206, 21G, etc., propylene oxide was added.

Tables XII, XIII and XIV give the data in regard to the oxyalkylation procedure as far as temperature and pressure are concerned and also give some data as to solubility of the oxyalkylated derivative in water, xylene and kerosene.

Referring to Table IX in greater detail, the data are as follows: The first column gives the example numbers, such as 1E, 2E, 3D, etc., etc.; the second column gives the oxyalkylation-susceptible compound employed which, as previously noted in the series 1E through 6E, is Example 1D, although it would b just as proper to say that in the case of 3E the oxyalkylation-susceptible compound was 1E, and in the case of 3B the oxyalkylation-susceptible compound was 2E. Actually reference is to the parent derivative for the reason that the figure stands constant and probably leads to a more convenient presentation. Thus, the third column indicates the polyepoxide-derived condensate previously referred to in the text.

The fourth column shows the amount of ethylene oxide in the mixture prior to the particular oxyethylation step. In the case of Example 1E there is no oxide used but it, appears, of course, in 2E, 3E and 4E, etc.

The fifth column can be ignored for the reason that it is concerned with propylene oxide only, and the sixth column can be ignored for the reason that it is concerned with butylene oxide only.

Th seventh column shows the catalyst which is invariably powdered caustic soda. The quantity used is indicated.

The eighth column shows the amount of solvent which is xylene unless otherwise stated.

The ninth column shows the amount of oxyalkylationsusceptible compound which in this series is the polyepoxide-derived condensate.

The tenth column shows the amount of ethylene oxide in at the end of the particular step.

Column eleven shows the same data for propylene oxide, and column twelve for butylene oxide. For obvious reasons these can be ignored in the series 1E through 18E.

Column thirteen shows the amount of the catalyst at the end of the oxyalkylation step, and column fourteen shows the amount of solvent at the end of the oxyalkylation step.

The fifteenth, sixtenth and seventeenth columns are concerned with molal ratio of the individual oxides to the oxyalkylation-susceptible compound. Data appears only in column fifteen for the reason, previously noted, that no butylene or propylene oxide were used in the present instance.

The theoretical molecular weight appears at the end of the table which is on the assumption, as previously noted, as to the probable molecular weight of the initial compound, and on the assumption that all oxide added during the period combined. This is susceptible to limitations that have been pointed out elsewhere, particularly in the patent literature.

Referring now to the second series of compounds in Table IX, to wit, Examples 19E through 36E, the situation is the same except that it is obvious the oxyalkylating agent used was propylene oxide and not ethylene oxide. Thus, the fourth column becomes a blank and the tenth column becomes a blank and the fifteenth column becomes a blank, but column five, which previously was a blank in Table IX now carries data as to the amount of propylene oxide present at the beginning of the reaction. Column eleven carries data as to the amount of propylene oxide present at the end of the reaction, and column sixteen carries data as to the ratio of propylene oxide to the oxyalkylation-susceptible compound. In all other instances the various headings have the same significance as previously.

Similarly, referring to Examples 37E through 54E in Table IX, columns four and five are blanks, columns ten and eleven are blanks, and columns fifteen and sixteen are blanks, but data appear in column six as to the butylene oxide present before the particular oxyalkylation step. Column twelve gives the amount of butylene oxide present at the end of the step, and column seventeen gives the ratio of butylene oxide to oxyalkylation-susceptible compound.

Table X is in essence the data presented in exactly the same way except the two oxides appear, to wit, ethylene oxide and propylene oxide. This means that there are only three columns in which data does not appear, all three being concerned with the use of butylene oxide. Furthermore, it shows which oxide was used first by the very fact that reference to Example 1F, in turn, refers to IE, and also shows that ethylene oxide was present at the very first stage. Furthermore, for ease of comparison and also to be consistent, the data under Molal Ratio in regard to ethylene oxide and propylene oxide goes back to the original diepoxide-derived condensate lb. This is obvious, of course, because the figures 64.8 and 49.2 coincide with the figures for 1E derived from ID, as shown in Table IX.

In Table X the same situation is involved except, of course, propylene oxide isused first and this, again, is perfectly apparent. Three columns only are blank, to wit, the three referring to butylene oxide. The same situation applies in examples such as 37F and subsequent examples where the two oxides used are ethylene oxide and butylene oxide, and the table makes it plain that ethylene oxide was used first. Inversely, Example 55F and subsequent examples show the use of the same two oxides but with butylene oxide being used first as shown on the table.

Example 73F and subsequent examples relate to the use of propylene oxide and butylene oxide. Examples beginning with 1G, Table XI, particularly 2G, 3G, etc.,

show the use of all three oxides so there are no blanks duplicated when used as intermediates subsequently for.

further reaction. It would be confusing to refer in too much detail in these various tables for the reason that all pertinent data appears and the tables are essentially selfexplanatory.

Reference to solvent and amount of alkali at any point takes into consideration the solvent from the previous step and the alkali left from this step. As previously pointed out, Tables XII, XIII and XIV give operating data in connection with the entire series, comparable to what has been said in regard to Examples 1E through 6E.

The products resulting from these procedures may contain modest amounts, or have small amounts, of the solvents as indicated by the figures in the tables. If desired, the solvent maybe removed by distillation, and particularly vacuum distillation. Such distillation also may remove traces or small amounts of uncombined oxide, if

36 Condensation of a nitrogenous product invariably yields a darker product than the original resin and usually has a reddish color. The solvent employed, if xylene, adds nothing to the color but one may use a darker colored present and volatile under the conditions employed. aromatic petroleum solvent. Oxyalkylation generally Obviously, in the use of ethylene oxide and propylene tends to yield lighter colored products and the more oxide oxide in combination one need not first use one oxide employed the lighter the color the product. Products and then the other, but one can mix the two oxides and can be prepared in which the final color is a lighter amber thus obtain what may betermed an indifferent oxyalkylaor straw color with a reddish tint. Such products can be tion, i. e., no attempt to selectively add one and then the decolorized by the use of clays, bleaching chars, etc. As other, or any other variant. far as use in demulsification is concerned, or some other Needless to y, 0116 Could Start With ethylene OXide industrial uses, there is no justification for the cost of and then use propylene oxide, and then go.back to bl hing the product. ethylene OXldC; or, inversely, start With propylene oxide, Generally Speaking, the amount of alkaline catalyst thefn use ethylene and f b ack Propyleng present is comparatively small and it need not be removed. oxide; one could a cqmbmainon m Whlch bun/1.6m: Since the products per se are alkaline due to the presence P 1.18mi along Wlth f one of two Oxldes of a basic nitrogen atom, theremoval of the alkaline ust. mentioned, or a combination of both of them. I

The Same would be true in regard to a mixture of catalyst 18 somewhat mole difiicult than ordinarily 1s the ethylene oxide and butylene oxide, or butylene Oxide and 20 case ror the reason that if one addshydrochlorlc acid, for propylene oxich example, to neutralize the alka llmty one may part1ally The colors of the pmducts usually vary from a reddish neutralize the basic nitrogen radical also. The preferred amber tint to a definitely red, amber and to a straw or light Procedure is to ignore the Presence of the alkali 11111688 Straw color, h reason i i -11 h no ff i it is objectionable or else add a stoichiometric amount made to obtain colorless resins initially and the resins f C tr hydrochl ric a d qual t th caustic themselves may be yellow, amber, or even dark amber. soda present.

TABLE IX Composition before Composition at end E Oxides Oxides Molal ratio X. :13 oso, viiit, oso, gg? ggf" ggf iiigii' No. lbs. EtO, PrO, BuO, lbs. lbs. lbs. EtO, PrO, BuO, lbs. lbs. a1 L alkyL alkyl' wt.

lbs. lbs. lbs. lbs. lbs. lbs. Suscent suscept Suscept.

empd cmpd. cmpd.

l l 9. 7 570 14. 1- 19. 4 4, 270 14. 35 38. 8 5, 670 14. 35 A. 58. 2 7, 070 14. 35 77. 6 8, 170 14. 35 155. 2 l3, 770 14. 9O 10. 4t 3, 730 14. 90 20. 8 4, 480 14. 90 41. 6 980 14. 90 62. 4 7, I 14. 90 83. 2 8, 980 14. 9O 166. 2 14, 930 13. 12. 5 3, 670 13. 85 25. 0 4, 570 13.85 37. 5 5, Q70 13. 85 62. f 7, 270 13. 85 100. O 9, 070 13. 85 150. 0 10, 870

TABLE XI Oompositlon before Composition at end E Oxides Oxides Molal Ratio X. No. 060, Oata- Sol- Gata- Sol- Theo.

Ex. S0, lyst, vent, 0S0, lyst, vent, EtOto PrO to BuOto mol. No. lbs. EtO, PrO, B110, lbs. lbs. lbs. EtO, PrO, B110, lbs. lbs. Oxy- Oxy- Oxy- Wt.

lbs. lbs. lbs. lbs. lbs. lbs. alkyl. alkyl. alkyl.

suscept. suscept. suscept. empd. cmpd. cmpd.

1G. 761?... 14.35 56.0 28.0 1.5 14.35 14.35 3.5 56.0 28.0 1.5 14.35 15.9 193.0 77.6 20,070 2G.. 7613... 14.35 3.5 56.0 28.0 1.5 14.35 14.35 7.0 56.0 28.0 1.5 14.35 31.8 193.0 77.6 20,770 3G.. 76F..- 14.35 7.0 50.0 28.0 1.5 14.35 14.35 14.0 56.0 28.0 1.5 14.35' 63.6 193.0 77.6 22,170 401.. 76F.-. 14.35 14.0 56.0 28.0 1.5 14.35 14.35 21.0 56.0 28.0 1.5 14.35 95.4 193.0 77.6 23,570 56.- 76F... 14.35 21.0 56.0 28.0 1.5 14.35 14.35 28.0 56.0 28.0 1.5 14.35 127.2 193.0 77.6 24,970 6G 76F... 14.35 28.0 56.0 28.0 1.5 14.35 14.35 56.0 56.0 28.0 1.5 14.35 254.4 193.0 77.6 30,570 7G.. 79F... 14.90 15.0 60.0 1.5 14.90 14.90 3.75 15.0 60.0 1.5 14.90 17.05 51.7 166.2 11,920 8G.. 791*... 14.90 3.75 15.0 60.0 1.5 14.00 14.90 7.50 15.0 60.0 1.5 14.90 34.10 51.7 166.2 12,670 99. 79F. 14.90 7.50 15.0 60.0 1.5 14.90 14.90 15.0 15.0 60.0 1.5 14.90 68.2 51.7 166.2 13,170 10G. 79F 14.90 15.0 15.0 00.0 1.5 14.90 14.90 22.5 15.0 60.0 1.5 14.90 102.3 51.7 166.2 14,670 11 791?... 14. 22.5 15.0 60.0 1.5 14.90 14.00 30.0 15.0 60.0 1.5 14.90 136.4 51.7 166.2 ,.170 12G. 79F... 14.90 30.0 15.0 60.0 1.5 14.00 14.00 60.0 15.0 60.0 1.5 14.90 272.8 51.7 166.2 22,.170 136.. 90F 13.85 60.75 54.0 2.0 13.85 13.85 6.75 60.75 54.0 2.0 13.85 30.7 209.25 15.0 24,370 14G.. 90F 13.85 6.75 60.75 54.0 2.0 13.85 13.85 13.50 60.75 54.0 2.0 13.85 61.4 209.25 15.0 ,71) 15G. 90F. 13.85 13.50 60.75 54.0 2.0 13.85 13.85 27.0 60.75 54.0 2.0 13.85 122.8 209.25 15.0 ,070 16G.. 90F. 13.85 27.0 60. 75 54.0 2.0 13.85 13.85 40.5 60.75 54.0 2.0 13.85' 184.2 209.25 15.0 29,770 17G.. 90F... 13.85 40.5 60.75 54.0 2.0 13.85 13.85 54.0 60.75 54.0 2.0 13.85 245.6 209.25 15.0 32,470 186.. 90F.-. 13.85 54.0 60.75 54.0 2.0 13.85 13.85 67.5 60.75 54.0 2.0 13.85 307.0 209.25 15.0 35,170 19G.. 58F... 14.35 14.0 14.0 1.5 14.35 14.35 14.0 14.0 14.0 1.5 14.35 63.6 48.25 38.8. ,270 20G 58F... 14.35 14.0 14.0 14.0 1.5 14.35 14.35 14.0 21.0 14.0 1.5 14.35 63.6 62.37 38.8 12,670 21G.. 5813... 14.35 14.0 21.0 14.0 1.5 14.35 14.35 14.0 28.0 14.0 1.5 14.35 63.6 96.5 38.8 14,070 22G.. 58F 14.35 14.0 28.0 14.0 1.5 14.35 14.35 14.0 35.0 14.0 1.5 14.35 63.6 120.62 38.8 15,470 23G 58F... 14.35 14.0 35.0 14.0 1.5 14.35 14.35 14.0 42.0 14.0 1.5 14.35 63.6 144.75 38.8 ,870 24G.. 58F". 14.35 14.0 42.0 14.0 1.5 14.35 14.35 14.0 49.0 14.0 1.5 14.35 63.6 168.87 38.8 210 25G.. 65F.-. 14.9 22.5 15.0 1.5 14.9 14.90 22.5 15.0 15.0 1.5 14.90 102.3 51.7 41.6 13:480 26G. 65F 14.9 22.5 15.0 15.0 1.5 14.9 14.90 22.5 22.5 15.0 1.5 14.90 102.3 77.55 41.6 14,980 27G. 65F... 14.9 22.5 22.5 15.0 1.5 14.9 14.90 22.5 30.0 15.0 1.5 14.90-102.3 103.4 41.6 16 481 28G 65F... 14.9 22.5 30.0 15.0 1.5 14.9 14.90 22.5 37.5 15.0 1.5 14.90 102.3 129.25 41.6 171980 29G 65F-.. 14.9 22.5 37.5 15.0 1.5 14.9 14.90 22.5 45.0 15.0 1.5 14.90 102.3 155.1 41.6 ,430 30G F 14.9 22.5 45.0 15.0 1.5 14.9 14.90 22.5 60.0 15.0 1.5 14.90 102.3 206.8 41.6 22,430 31G 72F... 41.4 41.4 27.0 1.5 13.85 13.85 41.4 13.5 27.0 1.5 13.85 188.4 46.6 62.5 18,2& 32G. 72F 41.4 41.4 13.5 27.0 1.5 13.85 13.85 41.4 13.5 27.0 1.5 13,85 188.4 46.6 62.5 18 250 336.. 72F 41.4 41.4 27.0 27.0 1.5 13.85 13.85 41.4 40.5 27.0 1.5 13.85 188.4 139.8 62.5 23 650 34G. 72F..- 41.4 41.4 40.5 27.0 1.5 13.85 13.85 41.4 47.25 27.0 1.5 13.85 188.4 163.1 62.5 2510(1) 35G. 72F..- 41.4 41.4 47.25 27.0 1.5 13.85 13.85 41.4 54.0 27.0 1.5 13.85 188.4 186.4 62.5 26,350 36G. 72F 41.4 41.4 54.00 27.0 1.5 13.85 13.85 41.4 60.75 27.0 1.5 13.85 188.4 209. 62.5 27,76)

TABLE XII Max. Max. Ex. No. te mp., pres Time,

WATER Kmosmm 130 10-15 Emulsifiable. Insoluble. 125-130 10-15 (10 D0.

10-15 10-15 10-15 10-15 10 15 10-15 10-15 10-15 10-15 10-15 10-15 10-15 10-15 10-15 10-15 10-15 10-15 10-15 10-15 10-15 10-15 10-15 10-15 10-15 10-15 D0. 10-15 2% Dispersible. 10-15 2% Soluble. 10-15 3% D0. 10-15 1% Insoluble. 1015 1% D0. 1015 D0. 10-15 2% Dispersible. 10-15 3% Soluble. 10-15 3% D0. 10l5 Insoluble 10-15 1 D0. 10-15 2 D0. 10-15 2% D0. 10-15 3 D0. 10-15 5 Soluble. 10-15 1 Insoluble 10-15 1% D0. 10-15 2% D0. 10-15 2% Do. 10-15 3 D0. 10-15 6 Soluble 10-15 1% Insoluble 10-15 2 D0. 10-15 2 D0. 10-15 4 D0. 10-15 4 D0. 10-15 5% Soluble. 

1. A PROCESS FOR BREAKING PETROLEUM EMULSION OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER, SAID DEMULSIFIER BEING OBTAINED BY A 3-STEP MANUFACTURING METHOD INVOLVING (1) CONDENSATION; (2) OXYALKYLATION WITH POLYEXPOXIDE: AND (3) OXYALKYLATION WITH A MONOEPOXIDE; SAID FIRST MANUFACTURING PROCESS BEING A STEP OF (A) CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NONOXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOWSTAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 